Azo dyestuffs



Patented Apr. 1, 1941 UNITED STATES PATE NT OFFICE AZO DYEST'UFFSWilfrid Herbert Clifi'e,

England, assignor to Im Blackley, Manchester, perial Chemical IndustriesLimited, a corporation of Great Britain N Drawing. Serial N 0.

Original application May 21, 1937, 144,099. Divided and this applicationApril 18, 1940, Serial No. 330,426. In Great Britain May 26, 1936 4Claims.

This invention relates to the manufacture of new azo dyestufis. Thisapplication is a division of my application Serial No, 144,099, filedMay 21,1937.

This invention has as an object to produce new azo dyestuffs. A furtherobject is to provide a new method of manufacturing azo dyes. A stillfurther object is to provide a new method of dye ing. Further objectswill appear hereinafter.

These objects are accomplished by the following invention. I have foundthat I can manufacture new azo dyestuffs by tetrazotizing 1 molecularproportion of a diamine of the general formula:

where both R and R' are phenylene or alkyl substituted phenylene and R."is alkyl, and coupling with 2 molecular proportions of the same or twodifferent coupling components.

An alternative method of manufacturing some of the new dyestufis is bydiazotizing, 1 molecular proportion of a nitroamine of the formula:

and R, R" and R have the significance given above, coupling with 1molecular proportion of a coupling component free from diazotizableamino groups, reducing the nitro group of the azo compound so obtained,and again diazotizing and coupling with 1 molecular proportion of thesame or a difierent coupling component.

The following examples illustrate but do not limit the invention:

I formula:

Example I 1 49B parts of 4 :4'-diaminobenzoyl-N-dodecyl- 'anilide aredissolved in 62.5 parts of 36% aqueous hydrochloric acid and 500 partsof water and tetrazotized at 5-10 C. with a solution of 17.2 parts ofsodium nitrite in 125 parts ofwater.

The resulting tetrazo solution is added gradually to an ice-coldsolution of 66 parts of the sodium.

salt of 2:8-aminonaphthol-fi-sulfonic acid and parts of anhydrous sodiumcarbonate in 600 parts of water. Coupling is rapid and a portion of thenew dyestufi so -formed separates out of solution. Salt is added toprecipitate the remainder and the dyestuif is filtered off and dried. Itdyes wool from a neutral or acid bath bright shades of red-brown andvery good fastness to washing and milling and to light. It has theprobable CuHzs OH Example II CuHsi Further examples of dyestuffsobtained according to the invention are given in the following table.

to be understood that I do not limit myself to the specific embodimentsthereof except as defined in the appended claims.

Diazo component Coupling components Shade on Wool4:4-diaminobenzoyl-N-dodecylanilide. 2rno1s. oil(4'-sulfophenyl)-3-methyl-5-pyrazolone Yellow. Do 2 mols. of2-naphthol-6-sulfonic acid. Orange. 2 mols. oi 2-naphthol-6z8 disulfonicac Do. 2 mols. of Z-naphthol-S-sulfonic acid. Do. 2 mols. of2-acetylamino-5-naphthol-7- Reddish-orange. 2 mols. of2acetylamino-8-naphtho1-6-sulf0nic acid Red. 2 mols. oil-naphtholA-sulionic acid. Scarlet 2 mols. of l-naphthol-Bzfi-disulfonicac Do. 2 mols. of l-acetylamino-S-naphthol-3zfi d Bluish-red. 2 mulls.off 22:Siamir;0napht1ol-6ul%nc aizfidfln Red-brown. I Y 1 mo o -p enyamino -nap t o -sn onic 'dlammobenzoyl'h'dodecylamhdem" {1 mol. of2:8-aminonephthol-3:6-disulfonic acid.

1 mol. of salicylic a cid D0 585 of p mtramlme Bluish-grccn.

- 1:S-uminonaphthol-Ii:6-disulfonic acid3:4'-diaminobcnzyol-N-cctylanilidc 2 mole of1-(2:5'-dichloro-4-sulfophenyl)-3-rncthyl-5- Yellow.

pyrazolone. 2 mols. of 2- aphthol-8-sulfon1c acid Orange. 2 mols. of2-naphthol-6:S-disulfonie acid Do. 2 mols. of l-naphthol-l-sulfonic acidScarlet 2 mols. oi l-(4-sullophenyl)-3-methy1-5-pyrazo1one, Yellow. 2mols. oi l-naphthol-i-sulfonic acid Scarlet. 2 mols. of2-N-beta-hydroxycthyl-amino-B-naphthol-6 Yellowish-brown.

sulionic acid.

2 mols. of l-(4-su1fophcnyl)-3-methyl-5-pyrazolone Yellow. 2 mols. of2:8-aminonaphthol-li-sulfonic acid Red-brown. 2 mols. of2-naphthol-B-sulionic acid Orange.

As coupling components I can use, for exam- I claim: ple, phenols,naphthols, naphtholsulfonic acids, 1. The compounds represented by theformula: naphthylamines, naphthylamme sulfonic acids, H g eraminonaphthols, their sulfonic acids or N-substituted derivatives,arylpyrazolones, arylpyrazolone sulfonic or carboxylic acids oracetoaceticarylamides. Also I may use as coupling components monoazocompounds such as, for example, the c o m p o u n d obtained by couplingdiazotized p-nitroaniline in mineral acid medium with 1:8-aminonaphthol-3 6-disulfonic acid.

Suitable diazo components may be obtained by nitrating, for example, a.benzoylor methylbenzoyl-alkyl-anilide or a nitrobenzoylalkylanilide andsubsequently reducing the dinitro compounds so-obtained eithercompletely to give the required diamines or partially to give therequired mononitroamines.

This invention is a valuable advance in the art as it gives newdyestuffs which dye wool from a neutral or acid bath to give dyeingswith very good fastness to light, milling, and washing.

As many apparently widely different embodiments of this invention may bemade without departing from the spirit and scope thereof, it is couplingcomponent.

2. The process which comprises azotizing the compound represented by theformula:

Higher alkyl and coupling it to an azo dyestufi coupling com- 4. Thecompound represented by the formula:

WHERE) HERBERT CLIFFE.

